Ethanolic Sodium Hydroxide Research Articles

Organophosphorus compounds. VI. The 'abnormal' Michaelis-Becker reaction. Diethyl 1-phenylepoxyethylphosphonate and diethyl 1-phenylvinylphosphate from diethyl phosphonate and phenacyl chloride

Phenacyl chloride reacts with sodium diethyl phosphonate in liquid ammonia solution to yield a 7 : 3 mixture of diethyl 1-phenylepoxyethylphosphonate (Ia) and the isomeric diethyl 1-phenylvinyl phosphate (IIa). Reaction of phenacyl chloride with diethyl phosphonate and triethylamine in benzene gives only diethyl 1-phenylvinyl phosphate. The action of hydrogen chloride on the epoxide (Ia) gives diethyl 2-chloro-1-hydroxy-1-phenylethylphosphonate (IV). This chlorohydrin reacts with sodium amide in liquid ammonia or with sodium hydroxide in ethanol to again yield a mixture of (Ia) end (IIa); with triethylamine in benzene, the product is mainly the vinyl phosphate (IIa).

The Theory of Shrinkproofing of Wool: Part V: Electron and Light Microscopy of Wool Fibers after Chemical Treatments

Lincoln 36's top, subjected to ten different chemical treatments as described in previous publications of this series [4, 5], was examined by light and electron microscopy using replica and thin-sectioning techniques. The sectioning and staining technique proved useful in showing the extent of penetration of the fiber by the reagent. The more drastic treatments such as 5% sodium hydroxide in water, hydrogen peroxide (10 vol for 16 hr), and severe treatment with chlorine (16% on weight of wool) caused almost complete obliteration of cellular detail throughout the fiber. Milder oxidation treatments may not have destroyed cellular detail, but may have oxidized sufficient disulfide bonds to prevent the TGA-OsO4 staining procedure from staining the matrix, with the result that the fine structure of microfibrils and matrix in the cortex were not visible. Alternative section staining procedures utilizing permanganate or lead hydroxide were also useful. Modification of the cuticle was observed after every treatment which effected shrinkproofing; namely, acid chlorination, treatment with permonosulfuric acid, hydrogen peroxide, sodium hydroxide, and treatment with permanganate in saturated salt. Some treatments (ethanol extraction, for example) produced a marginal degree of shrinkproofing and showed a small amount of cuticle modification. Other treatments (with peracetic acid, for instance) did not modify the cuticle and did not effect shrinkproofing. Thus, the primary requirement for shrinkproofing by degradative chemical treatments is sufficient modification of the fiber cuticle. The chemical reaction by which cuticle modification (and thereby shrinkproofing) is brought about generally involves cystine, but with the use of ethanolic sodium hydroxide the major process is probably the removal of a wool wax constituent from the cell membrane complex beneath the cuticle. Although modification of the cortex by chemical reaction is undesirable from a practical point of view, it has only a secondary effect on the degree of shrinkproofing. Various methods of confining the reaction to the cuticle are discussed. In particular, it was found that sodium hydroxide in water penetrates throughout the fiber, whereas the reaction was limited to the cuticle by the use of sodium hydroxide in ethanol or in an aqueous solution saturated with salt. Similarly, reaction of the cortex occurred with permanganate in water (with no subsequent shrinkproofing), whereas the presence of salt limited the reaction to the cuticle, thus producing shrinkproofing. The correlation between cuticle modification (hence degree of shrinkproofing) and alteration of frictional coefficients was good in most cases, but the lack of correlation in a few cases emphasized the importance of a new approach to the measurement of frictional coefficients.

Increasing the Felting Rate of Wool

Treatment with acid solutions of iodate or chlorate increases the rate of felting of wool in soap solution by about 30%. Reagents used for carroting rabbit fur, such as mercuric nitrate in nitric acid, peracetic acid, or alkaline thioglycolate, increase felting rate but cause severe damage. Acid and alkaline peroxide, acid chlorine, hypochlorite at pH 8, ethanolic sodium hydroxide, persulfate, and acid bromate can all produce a small increase in felting rate under mild conditions of treatment, but more severe treat ment decreases the felting rate. Permanganate/saturated salt, permanganate/water, permanganate/hypochlorite, and permonosulfuric acid treatments do not give increased felting rate under any conditions. , The best treatments found for increasing felting are those with acid iodate or chlorate, but these would be too expensive, for the limited increase in felting rate , obtained, to be useful industrially. Increased felting appears to be due to weakening of fibers by extensive reaction of the reagent with cortex rather than to changes in frictional properties. Decreased felting seems logicall to be due to reaction with cuticle, but a large decrease in felting rate can be obtained with a relatively small change in the difference between anti- and with-scale frictional coefficients (0.29 to 0.22), as measured by the capstan method. Reaction does not have to be confined to, or concentrated at, the surface of fibers to decrease felting rate. All that is necessary is that a sufficient degree of modification of cuticle be obtained, with or without extensive modification of cortex. Industrially useful shrinkproofing reagents are those which are sufficiently reactive to give cuticle modification when low concentrations are used and thus when over-all reaction and damage are correspondingly low.

The Effect of pH and Detergents on the Felting of Shrink-Resistant Wool

The rate of felting of an untreated wool fabric increases with decreasing pH of the felting solution over the pH range 2-10. The felting rate is increased at all pH values by the addition of nonionic detergent to the solution. The felting, relative to untreated wool, of wool made shrink-resistant with perman ganate/salt, acid chlorine, permonosulfuric acid followed by sulfite, permanganate hypo chlorite, peracetic acid/hypochlorite, hypochlorite at pH 8, or gaseous chlorine increases with decreasing pH of the felting solution. The magnitude of this effect can he reduced by treatment with higher concentrations of reagents. After treatment with reagents of the concentrations used industrially, no change in felting rates with pH can be de tected at pH values above 5. The actual rate of felting of wool treated with reagents of these concentrations is low and is not significantly affected by the addition of soap or nonionic detergents to the solutions. The felting, relative to untreated wool, of wool treated with ethanolic thioglycolate, aqueous hisulfite (on extracted wool). hydrogen peroxide folluwed hy bisulfite, ethanolic sodium hydroxide, or sodium hydroxide saturated salt does not vary with pH in the absence of detergent. Felting is increased by the addition of detergent to the solutions. In detergent solutions, the relative felting of wool treated with ethanolic thioglycolate, aqueous bisulfite (on extracted wool), or hydrogen peroxide bisulfite does not change with pH. hut the relative felting of wool treated with sodium hydroxide in ethanol or saturated salt solution reaches a maximum at pH 7-9. Frictional properties of fibers treated with some of the reagents have been measured (by the capstan method using a keratin rod at different pH values in the presence and absence of detergent. Felting behavior does not appear to be explained by these fric tional properties alone. Some other property, or properties, of treated wool, which vary differently with pH than do similar properties of untreated wool, must play a part in felting.

The action of oxygen corona and of ozone on polyethylene

AbstractFilms of low‐density polyethylene which were exposed to a corona discharge in oxygen at a pressure of 1 atm. lost weight and decreased in thickness due to oxidation of the surface to volatile products (principally carbon dioxide and water). The weight loss was directly proportional to the time of exposure and was independent of film thickness. The infrared spectra of the films after exposure to the discharge showed a strong band at 1717 cm.–1 due to carbonyl groups. After a short time in the discharge, the formation of new carbonyl groups in the polymer was balanced by their destruction by oxidation to volatile products at the surface. The intensity of the carbonyl band initially increased rapidly with increasing exposure, but reached a maximum value after 4 hr. and then showed no further change for 90 hr., during which time the thickness of a film originally 4 mils thick was reduced to approximately 1 mil. The data indicate that the carbonyl groups are present in a relatively thin oxidized layer, estimated to be between 5 X 102 and 7 X 104 A. in depth. Carbonyl groups were also formed in films which were not in the discharge area but were exposed to the ozone produced by the discharge. The position of the carbonyl band in both types of oxidized film is consistent with either carboxylic acids or ketone. The relative amounts of the two were determined by soaking the films in ethanolic sodium hydroxide solution to convert the acid to carboxylate ion and measuring the decrease in intensity of the 1717‐cm.–1 band. In the sample which was exposed to the discharge, 60% of the carbonyl was carboxylic acid and 40% was ketone. In the sample exposed only to ozone, the proportion was 30% acid and 70% ketone. It is believed that the carbonyl groups in both cases are the result of attack of ozone on the carbon‐carbon double bonds of the polymer. Small amounts of oxalic acid and other low molecular weight acids were also produced in films exposed to the discharge, presumably due to oxidation of the surface by one or more of the unstable species of the corona.

ヒノリン誘導体について その4

1) Quinaldic acid hydrazide was reacted with various aldehydes to form the corresponding hydrazones (I to XIII), (XVI) was reacted with 2-nitrofurfural, p-dimethylaminobenzaldehyde, p-hydroxybenzaldehyde, and p-acetamidobenzaldehyde to form the corresponding hydrazones (XVII to XX), and (I) and (VII) were led to their acetylated compounds (XIV and XV) by treatment with acetic anhydride.2) Oxidation of quinaldic acid with hydroxide in acetic acid solution or hydrolysis of quinaldonitrile 1-oxide with sodium hydroxide in ethanol afforded (XXI). Hydrolysis of (XXIII) with ethanolic sodium hydroxide results in deoxygenation to form cinchoninc acid. Therefore, (XXIII) was converted to (XXV) by the Radziszewsky's method, then to (XXVI) with sulfuric acid and sodium nitrite, and (XXI) and (XXVI) were esterified with diazomethane to be converted to (XXVII) and (XXVIII). Reaction of these with hydrazine hydrate afforded the hydrazides (XXIX and XXX). Condensation of (XXX) with p-dimethylaminobenzaldehyde and p-hydroxybenzaldehyde, and that of (XXX) with p-dimethylaminobenzaldehyde afforded the corresponding hydrazones (XXXI to XXXIII) Examinations were made of the antibacterial power of these compounds against the most potent human-type tubercle bacilli, Frankfurt strain.

Toxic Protein Degradation Products

SummaryToxic polypeptides, similar to those obtained by Vaughan(1), have been prepared by treatment of certain proteins with boiling 2% ethanolic sodium hydroxide. These substances are soluble in water and in ethanol, are capable of dialyzing through a cellophane membrane and have been shown to be a mixture of essentially basic polypeptides of similar composition. Their characteristic absorption at 270–280 mμ does not appear to be related to their toxic properties. At an amino acid level the polypeptides differ from their parent proteins in that they contain little or no cystine, serine or threonine. The most toxic preparations, obtained by a salting out procedure, followed by dialysis or by ion exchange chromatography, while nontoxic when given orally were lethal to guinea pigs at a level of 0.5 mg/kg intravenously. Pretreatment of the animals with atropine, epinephrine or Neo-Antergan failed to prevent or modify the effect of a lethal dose of the polypeptide thus excluding liberation of histamine or ace...

Equilibrium between Ethoxide and Hydroxide Ions in Ethanol

THERE is some evidence1,2 that, in solutions made by dissolving sodium hydroxide in ethanol, much of the hydroxyl ion is replaced by ethoxide, the equilibrium OH− + EtOH ⇌ OEt− + H2O lying well to the right. We have confirmed this by measuring the equilibrium constant K = [OEt−][H2O]/[OH−][EtOH] at 25° C, using solutions made by dissolving sodium or sodium hydroxide in ethanol–water mixtures containing 10–50 per cent water by weight. The method adopted makes use of the fact that trinitrotoluene ionizes to give an intensely coloured ion in the presence of ethoxide3. The concentration of ethoxide ion in the solutions can thus be determined colorimetrically, and that of hydroxide ion can then be found by determining the total base concentration by titration.

POLARIMETRIC DETERMINATION OF STARCH IN CEREAL PRODUCTS: IV. CRITICAL STUDIES OF METHODS FOR THE DETERMINATION OF STARCH IN WHOLE WHEAT, GRANULAR, AND PATENT FLOURS

A rapid polarimetric method applicable to whole wheat, granular, and patent flour is described in which the starch is dissolved in hot calcium chloride solution under uniform conditions, soluble proteins being removed by the addition of stannic chloride or uranyl acetate prior to volume adjustment, filtration, and polarization.Approximately 2.5-gm. samples (40 mesh) are placed in tall beakers and suspended uniformly in 10 cc. of water. Calcium chloride solution (60 cc., d. 1.30, pH 5.5) and 2 cc. of 0.8% acetic acid are added. The mixture is boiled at constant salt concentration for 15 min., foaming being prevented by dropwise addition of n-octanol as required. After cooling, 2.5 to 5.0 cc. of 4% stannic chloride or 10 cc. of 5% uranyl acetate (each dissolved in calcium chloride solution) is added, the mixture is diluted to 100 cc. with calcium chloride solution, mixed, and filtered. After discarding the first portion, the filtrate is polarized in 2 dm. tubes. [α]D = + 203° is used in the calculations; % starch = 2 dm. reading in degrees × 10 when 2.463 gm. flour samples are employed.Stannic chloride is shown to depress the specific rotation value of starches. A large error is introduced when it is used on wheat flour in the amount prescribed by Mannich and Lenz. Using the above uranyl acetate treatment, starch may be rapidly determined in corn, barley, rye, rice, grain sorghum, and buckwheat by the calcium chloride polarimetric method. It is shown that interfering wheat proteins may be removed by preparatory extraction with aqueous ethanol and dilute sodium hydroxide, as well as by precipitation. The latter being more rapid is judged most suitable for routine applications. Levorotatory hemicelluloses of bran and endosperm are dissolved in considerable amount by boiling calcium chloride solution but their small effect is balanced by the error of overestimation arising from insoluble wheat solids. Hemicelluloses are shown to be capable of causing high results in applications of the diastase–hydrochloric-acid method to wheat products. The improved calcium chloride polarimetric method is considered the most reliable of existing macro-methods for the determination of starch in wheat.